CN110072897B - Polypropylene composition with low seal initiation temperature and high melting temperature - Google Patents

Polypropylene composition with low seal initiation temperature and high melting temperature Download PDF

Info

Publication number
CN110072897B
CN110072897B CN201780076833.8A CN201780076833A CN110072897B CN 110072897 B CN110072897 B CN 110072897B CN 201780076833 A CN201780076833 A CN 201780076833A CN 110072897 B CN110072897 B CN 110072897B
Authority
CN
China
Prior art keywords
polypropylene composition
propylene
ppf1
propylene polymer
comonomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201780076833.8A
Other languages
Chinese (zh)
Other versions
CN110072897A (en
Inventor
L.博拉格诺
P.莱斯基宁
L.雷斯科尼
M.霍夫
F.伯格
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Borealis AG
Original Assignee
Borealis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Borealis AG filed Critical Borealis AG
Publication of CN110072897A publication Critical patent/CN110072897A/en
Application granted granted Critical
Publication of CN110072897B publication Critical patent/CN110072897B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6491—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon
    • C08F4/6492—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/651—Pretreating with non-metals or metal-free compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6546—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof organo-magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst

Abstract

The present invention relates to a polypropylene composition having a low Seal Initiation Temperature (SIT) and a high melting point (Tm), thus having a wide sealing window.

Description

Polypropylene composition with low seal initiation temperature and high melting temperature
Technical Field
The present invention relates to polypropylene compositions having improved low sealing temperatures and high melting temperatures. The invention also relates to a process for making said polypropylene composition into an article, in particular a film comprising said polypropylene composition, and to the use of the composition for its manufacture.
Background
Propylene homopolymers and copolymers are suitable for a variety of applications such as packaging, textiles, automotive and pipe. The packaging industry is an important field of application for propylene polymers. In particular, for film applications such as heat sealing, sealing performance is critical.
Heat sealing is the primary method of making flexible and semi-rigid packages. Important features of good sealing are as follows:
a) low Seal Initiation Temperature (SIT), which is required to support high speed operation of the packaging machine,
b) a wide sealing window, which is especially desirable for processing windows on HFFS (horizontal form, fill, and seal) packaging lines, and
c) an additional high melting point, which is important for e.g. biaxially oriented pp (BOPP), to avoid sticking and blocking and to achieve high BOPP line speeds.
Operating at lower temperatures has the benefit that the article to be sealed is not subjected to high temperatures, and thus a low SIT is advantageous to ensure a rapid seal. The lower temperature is obviously less expensive to form and maintain, and thus also has economic advantages.
Avoiding high sealing temperatures has other advantages, particularly when packaging temperature sensitive items.
In the field of polyolefin films, the properties possessed by a particular type of film generally result from the polyolefin composition of which the film is comprised. Thus, polyolefin compositions having a low Seal Initiation Temperature (SIT) and a high melting point are generally desired.
WO2011064119 discloses a polyolefin composition for preparing heat-sealable films comprising a propylene copolymer and other polyolefin components, in particular, the polyolefin composition comprises (all percentages are by weight):
a)60 to 94% of one or more copolymers of propylene with one or more comonomers selected from ethylene, C4-C8Alpha-olefins and combinations thereof, wherein the content of one or more comonomers in (a) is from 5 to 25%, preferably from 7 to 20%;
b)2 to 20% of one or more 1-butene homopolymers or copolymers;
c)1 to 20% of an elastic or plastic polyolefin or polyolefin composition.
The polymerized comonomer is statistically distributed in the resulting copolymer. By mixing a large amount of a specific propylene copolymer with a butene-1 polymer, an elastomeric or plastic polyolefin or a polyolefin composition, a balance of heat sealability (very low seal initiation temperature) and optional properties (in particular low haze) is achieved.
The composition of WO2011064119 has different components from the composition of the present invention. In addition, the composition of WO2011064119 shows that a low onset temperature is achieved by at least three components in the composition. The object of the present invention is to solve one or more of the above problems, and in particular to provide a simpler composition with a low sealing temperature and a high melting point.
Whatever the type of polymer, at most all the desired end properties must be met and, in addition, must be easy to process, i.e. must withstand the effects of stress. However, there is often a conflict between final properties and processability. It is often the case that an improvement in achieving one desired property comes at the expense of the other.
Thus, there remains a need to design materials that achieve a better balance between high melting point and low Seal Initiation Temperature (SIT) and thus have a wide sealing window and thermal stability.
Disclosure of Invention
The present invention is based on the following findings: the above-mentioned requirements for heat seal applications, i.e. simultaneously a better balance between high melting point and low Seal Initiation Temperature (SIT), wide sealing window and thermal stability, can be achieved by specially designed polyolefin compositions.
Thus, the present invention provides a polypropylene composition which is a binary mixture comprising two propylene polymer components PPF1 and PPF2, the specific contents of said two components being as follows:
a) less than or equal to 50 wt% of a propylene polymer component PPF1, which is a propylene copolymer comprising propylene monomers and 1.50 to 7.00 mol% of a monomer selected from C4-C10A comonomer of an alpha-olefin, and
b) greater than or equal to 50 wt% of a propylene polymer component PPF2 which is a propylene terpolymer comprising propylene monomer, from 3.00 to 12.00 mol% of ethylene comonomer and from 1.50 to 17.00 mol% of a comonomer selected from C4-C10One of the comonomers of the alpha-olefin,
characterized in that the polypropylene composition:
i. has a melting temperature (Tm) in the range of 135 to 160 ℃ (determined by DSC according to ISO 11357),
satisfying the following equation:
△＝Tm-SIT
wherein Δ is in the range of 39 to 50 ℃, and wherein
Tm is the melting temperature of the polypropylene composition according to the invention, in units of,
SIT is the seal initiation temperature of the polypropylene composition in degrees Celsius, calculated from pellets by DSC measurement according to the method described in the methods of measurement section herein,
the amounts of PPF1 and PPF2 were calculated relative to the total amount of propylene polymer components PPF1 and PPF 2.
The polypropylene composition according to the present invention is a binary mixture comprising, preferably consisting of, the propylene polymer component PPF1 and the propylene polymer component PPF2, and the propylene polymer component PPF1 and the propylene polymer component PPF 2. The results obtained are particularly good when the propylene polymer components PPF1 and PPF2 are present in specific amounts.
Less than or equal to 50 wt%, preferably from 30 to 50 wt%, more preferably from 35 to 50 wt% of the propylene polymer component PPF1 is present in the polypropylene composition according to the invention. The amount of PPF1 was calculated relative to the total amount of propylene polymer components PPF1 and PPF 2.
Greater than or equal to 50 wt%, preferably from 50 to 70 wt%, more preferably from 50 to 65 wt% of the propylene polymer component PPF2 is present in the polypropylene composition according to the invention. The amount of PPF2 was calculated relative to the total amount of propylene polymer components PPF1 and PPF 2.
The propylene polymer component PPF1 is typically a propylene copolymer comprising a monomer selected from C4-C10A comonomer of alpha-olefins, preferably selected from C4-C8A comonomer of alpha-olefins, more preferably selected from C4-C6A comonomer of alpha-olefins, even more preferably 1-butene (C)4)。
The propylene copolymer (PPF1) generally contains 1.50 to 7.00 mol%, preferably 2.30 to 6.10 mol%, more preferably 3.00 to 5.40 mol% of C4-C10Alpha-olefin comonomer units. C4-C10The amount of alpha-olefin comonomer units is calculated relative to the total amount of monomers in the propylene copolymer (PPF 1).
Typically, the Melt Flow Rate (MFR) of the propylene copolymer (PPF1)2) Less than or equal to 10.0g/10 min. MFR of propylene copolymer (PPF1)2Measured according to ISO 1133 at 230 ℃ and 2.16kg load. MFR of propylene copolymer (PPF1)2Preferably 3.0 to 10.0g/10min, more preferably 4.0 to 9.0g/10 min. A suitable lower limit is 3.0g/10min, preferably 4.0g/10 min. A suitable upper limit is 10.0g/10min, preferably 9.0g/10 min. The upper and lower limits of the range are included.
The propylene polymer component PPF2 is typically a propylene terpolymer comprising ethylene comonomer and C4-C10A comonomer of alpha-olefin, preferably ethylene comonomer and selected from C4-C8A comonomer of alpha-olefins, more preferably an ethylene comonomer and a comonomer selected from C4-C6A comonomer of alpha-olefins, even more preferably an ethylene comonomer and 1-butene (C)4)。
Propylene terpolymers (PPF2) generally contain from 3.00 to 12.00 mol%, preferably from 3.00 to 9.00 mol%, more preferably from 3.00 to 7.50 mol% of ethylene comonomer units. The amount of ethylene comonomer units is calculated relative to the total amount of monomers in the propylene terpolymer (PPF 2).
The propylene terpolymer (PPF2) generally contains 1.50 to 17.00 mol%, preferably 3.50 to 16.00 mol%, more preferably 5.00 to 15.00 mol% of C4-C10Alpha-olefin comonomer units. C4-C10The amount of alpha-olefin comonomer units is calculated relative to the total amount of monomers in the propylene terpolymer (PPF 2).
Typically, the Melt Flow Rate (MFR) of the propylene terpolymer (PPF2)2) Less than or equal to 10.0g/10 min. MFR of propylene terpolymer (PPF2)2Calculated according to the method described in the measurement methods section herein. MFR of propylene terpolymer (PPF2)2Preferably 3.0 to 10.0g/10min, more preferably 4.0 to 9.0g/10 min. A suitable lower limit is 3.0g/10min, preferably 4.0g/10 min. A suitable upper limit is 10.0g/10min, preferably 9.0g/10 min. The upper and lower limits of the range are included.
The polypropylene composition typically contains a total amount of ethylene comonomer units of 1.50 to 6.00 mol%, preferably 1.50 to 4.50 mol%, more preferably 1.50 to 3.70 mol%. The amount of ethylene comonomer units is calculated with respect to the total amount of monomers in the polypropylene composition.
The polypropylene composition generally contains C in a total amount of 3.80 to 12.00 mol%, preferably 4.60 to 11.00 mol%, more preferably 5.30 to 10.50 mol%4-C10Alpha-olefin comonomer units. C4-C10The amount of alpha-olefin comonomer units is calculated with respect to the total amount of monomers in the polypropylene composition.
Generally, the Melt Flow Rate (MFR) of the Polypropylene composition according to the invention2) Is 3.0 to 10.0g/10 min. MFR of the polypropylene composition2Measured according to ISO 1133 at 230 ℃ and 2.16kg load. MFR of the polypropylene composition2Preferably 4.0 to 9.0g/10min, more preferably 5.0 to 8.0g/10 min. A suitable lower limit is 3.0g/10min, preferably 4.0g/10min, more preferably 5.0g/10 min. A suitable upper limit is 10.0g/10min, preferably 9.0g/10min, more preferably 8.0g/10 min. The upper and lower limits of the range are included.
Typically, the polypropylene composition according to the present invention has a Seal Initiation Temperature (SIT) of from 85 to 110 ℃, preferably from 90 to 105 ℃, more preferably from 95 to 100 ℃. Seal Initiation Temperature (SIT) was calculated from the pellets by DSC measurement as described in the measurement methods section herein.
Typically, the polypropylene composition according to the present invention has a melting temperature (Tm) of 135 to 160 ℃, preferably 137 to 155 ℃, more preferably 140 to 150 ℃. Melting temperature (Tm) was determined by DSC according to ISO 11357.
Typically, the polypropylene composition according to the present invention has a xylene soluble fraction (XS) of from 15 to 40 wt%, preferably from 15 to 35 wt%, more preferably from 15 to 30 wt%. The xylene-soluble fraction is determined at 25 ℃ according to ISO 16152, fifth edition, 2005-07-01.
Generally, the polypropylene composition according to the present invention satisfies the following equation (1):
Tm-SIT equation (1)
Wherein Δ is in the range of 39 to 50 ℃, and wherein
Tm is the melting temperature of the polypropylene composition according to the invention, in units of,
SIT is the seal initiation temperature calculated from the pellets by DSC measurement according to the method described in the measurement methods section herein.
The value Δ according to equation (1) is preferably in the range of 40 to 48 ℃, more preferably in the range of 41 to 46 ℃.
The invention also provides a polypropylene composition according to the invention, characterized in that the propylene polymer component PPF1 is a propylene polymer comprising 1-butene (C)4) The propylene polymer component PPF2 is a copolymer comprising ethylene comonomer and 1-butene (C)4) The propylene terpolymer of (1).
The polypropylene composition according to the present invention can be prepared by (melt) mixing the individual propylene polymer components PPF1 and PPF2, i.e. the propylene copolymer (PPF1) and the propylene terpolymer (PPF2) according to the present invention. Thus, the propylene polymer components PPF1 and PPF2 comprised in the polypropylene composition according to the invention may be prepared in separate polymerization processes and then mixed, for example, in a mixing device, preferably in a melt mixing device such as an extruder. During the mixing process, suitable additives may be additionally added.
The polypropylene composition according to the present invention may be prepared in a polymerization process. Thus, the propylene polymer components PPF1 and PPF2 were produced in the polymerization process.
The polymerization process suitable for preparing the polypropylene composition of the present invention generally comprises at least two polymerization stages, each of which can be carried out in solution, slurry, fluidized bed, bulk or gas phase. In one embodiment, the polymerization process comprises at least one bulk reactor stage (e.g. slurry or loop reactor stage) and at least one gas phase reactor stage, each stage comprising at least one reactor and all reactors arranged in cascade. In a particularly preferred embodiment, the polymerization process comprises at least one bulk reactor and at least one gas phase reactor and is arranged in this order.
In some further preferred embodiments, the polymerization process comprises one bulk reactor (e.g. slurry reactor or loop reactor) and at least one gas phase reactor (e.g. one or two gas phase reactors). The polymerization process may also include a pre-reactor stage and a post-reactor stage. The pre-reactor stage typically comprises a pre-polymerization reactor. In such polymerization processes, high polymerization temperatures are generally employed in order to achieve specific properties of the resulting propylene copolymers. Typical temperatures in the process are 60 ℃ or higher, preferably 80 ℃ or higher, more preferably 85 ℃ or higher. The high polymerization temperatures described above may be employed in some or all of the reactors in the cascade.
A preferred polymerization process is a "loop-gas phase" process, such as BORSTAR developed by BorealisTMProvided is a technique. Examples of such polymerization processes are described in EP0887379, WO92/12182, WO2004/000899, WO2004/111095, WO99/24478, WO99/24479 and WO 00/68315.
The present invention also relates to a most preferred process for the preparation of the polypropylene composition of the present invention by a sequential polymerization process comprising at least two reactors in series, said process comprising the steps of:
in the first reactor (R-1), which is a slurry reactor, preferably a loop reactor, propylene and a catalyst selected from the group consisting of C4-C10One of the comonomers of the alpha-olefin is polymerized to give the propylene polymer component (PPF1), which is the propylene copolymer according to the invention,
transferring the propylene polymer component (PPF1) and unreacted comonomer from reactor (R-1) to a second reactor (R-2), which is a first gas phase reactor-1 (GPR-1),
in the gas-phase reactor-1 (GPR-1), propylene, ethylene and a gas phase catalyst selected from the group consisting of4-C10One comonomer of an alpha-olefin is polymerized in the presence of a propylene polymer component (PPF1) to obtain a propylene polymer component (PPF2) which is a propylene terpolymer according to the present invention, said propylene polymer componentThe component (PPF2) and the propylene polymer component (PPF1) form a polypropylene composition according to the invention,
recovery of the polypropylene composition according to the invention.
After the end of the polymerization in gas phase reactor-1 (GPR1), the polypropylene composition according to the invention was recovered by conventional processes. The polypropylene composition according to the invention as recovered is generally in the form of pellets. The resulting polypropylene composition in the form of pellets can be pelletized in a conventional compounding extruder using various additives such as stabilizers, antioxidants, ultraviolet absorbers, antistatic agents and slip agents. Typically, the polypropylene composition according to the present invention may comprise not more than 5.0 wt%, more preferably not more than 3.0 wt%, such as not more than 2.0 wt% of said additives.
A polymerization catalyst is generally present in the polymerization preparation process according to the invention. The polymerization catalyst may be a metallocene catalyst or a ziegler-natta catalyst. Typically, ziegler-natta catalysts comprise one or more compounds of a group 4 to 6 Transition Metal (TM), such as titanium, as defined in IUPAC (2013 version), as well as compounds of a group 2 metal (e.g. magnesium compounds) and an Internal Donor (ID).
The catalyst component may be supported on a particulate support, for example an inorganic oxide such as silica or alumina. Alternatively, the magnesium halide may also constitute a solid support. It is also possible to not support the catalyst component on an external support, but to prepare the catalyst by emulsion curing or deposition as is well known to those skilled in the art of catalyst preparation.
Preferably, a specific type of Ziegler-Natta catalyst is present in the polymerization process according to the present invention. In this particular type of Ziegler-Natta catalyst, it is essential that the internal donor be a non-phthalic compound. Preferably, no phthalate compound is used throughout the preparation of the specific type of Ziegler-Natta catalyst, so that the final specific type of Ziegler-Natta catalyst does not contain any phthalate compound. Thus, the propylene polymer components PPF1 and PPF2 are free of phthalic acid based compounds.
In general, the specific type of ZieglerThe natta catalysts comprise an Internal Donor (ID) selected to be a non-phthalic compound, in such a way that the specific type of ziegler-natta catalyst is completely free of undesired phthalic compounds. Furthermore, a specific type of ziegler-natta catalyst may be a solid catalyst, which preferably does not contain any external support material, such as silica or MgCl2Etc., so that the solid catalyst is of a self-supporting type.
The solid catalyst can be obtained by the following general process flow:
a) providing a solution of:
a1) At least one group 2 metal alkoxide (Ax) which is the reaction product of a group 2 metal compound and an alcohol (a) optionally in an organic liquid reaction medium which includes at least one ether moiety in addition to a hydroxyl moiety; or
a2) At least one group 2 metal alkoxide (Ax') which is the reaction product of a group 2 metal compound with said alcohol (a) and an alcoholic mixture of a monoalcohol of formula ROH, optionally in an organic liquid reaction medium; or
a3) A mixture of said group 2 metal alkoxide (Ax) and a group 2 metal alkoxide (Bx), compound (Bx) being the reaction product of a group 2 metal compound and a monohydric alcohol (B), optionally in an organic liquid reaction medium; or
a4) The general formula is M (OR)1)n(OR2)mX2-n-mOR a group 2 metal alkoxide M (OR) of1)n’X2-n’And M (OR)2)m’X2-m’Wherein M is a group 2 metal, X is a halogen element, R1And R2Is different alkyl of 2-16 carbon atoms, n is more than or equal to 0<2、0≤m<2 and n + m + (2-n-m) ═ 2, provided that n and m are not 0 at the same time, 0<n' is less than or equal to 2 and 0<m’≤2；
b) Adding the solution of step a) to at least one compound of a group 4 to 6 transition metal; and
c) obtaining particles of the solid catalyst component, adding a non-phthalic internal electron donor (ID) in at least one step prior to step c).
The Internal Donor (ID) or a precursor thereof is preferably added to the solution of step a) or to the transition metal compound before the addition of the solution of step a).
According to the above process scheme, the solid catalyst can be obtained by a deposition method or an emulsion-solidification method depending on the physical conditions, in particular the temperatures used in steps b) and c). Emulsions are also known as liquid-liquid two-phase systems. In both processes (deposition or emulsion-curing), the catalyst chemistry is the same.
In the precipitation process, the mixing of the solution of step a) with the at least one transition metal compound of step b) is carried out such that the entire reaction mixture is maintained at a temperature of at least 50 ℃, more preferably in the range of 55 ℃ to 110 ℃, more preferably in the range of 70 ℃ to 100 ℃ to ensure complete precipitation of the catalyst component as solid catalyst component particles (step c).
In the emulsion-curing process, the solution of step a) is added to the at least one transition metal compound in step b), generally at a relatively low temperature, such as from-10 ℃ to less than 50 ℃, preferably from-5 ℃ to 30 ℃. During the stirring of the emulsion, the temperature is generally maintained at-10 ℃ to less than 40 ℃, preferably-5 ℃ to 30 ℃. The emulsion dispersed phase droplets form the active catalyst component. The solidification of the droplets is suitably carried out by heating the emulsion to a temperature of 70-150 c, preferably 80-110 c (step c). The present invention preferably uses a catalyst prepared by an emulsion curing process.
In step a), preference is given to using a2) Or a3) I.e. a solution of (Ax') or a mixture of (Ax) and (Bx).
The group 2 metal is preferably magnesium. The magnesium alkoxide compounds (Ax), (Ax') and (Bx) may be prepared in situ in the first step of the catalyst preparation process, step a), by reacting a magnesium compound with one or more alcohols as described above. Another option is to prepare the magnesium alkoxide compound separately or even to make available a ready-made magnesium alkoxide compound commercially and use it as such in the catalyst preparation process of the present invention.
An illustrative example of the alcohol (a) is ethylene glycol monoether. Preferred alcohols (A) are C2-C4Ethylene glycol monoethers, wherein the ether moiety comprises 2 to 18 carbon atoms, preferably 4 to 12 carbon atoms. Preferred examples are 2- (2-ethylhexyloxy) ethanol, 2-butoxyethanol, 2-hexyloxyethanol, 1, 3-propanediol-monobutyl ether and 3-butoxy-2-propanol, of which 2- (2-ethylhexyloxy) ethanol, 1, 3-propanediol-monobutyl ether and 3-butoxy-2-propanol are particularly preferred.
Exemplary monoalcohols (B) are represented by the general structural formula ROH, wherein R is a straight or branched chain C2-C16Alkyl residue, preferably C4-C10Alkyl residue, more preferably C6-C8An alkyl residue. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.
Preferably, a mixture of magnesium alkoxide compounds (Ax) and (Bx) or a mixture of alcohols (a) and (B), respectively, is used in the following molar ratios: bx: Ax or B: A is 10:1 to 1:10, more preferably 6:1 to 1:6, even more preferably 5:1 to 1:3, most preferably 5:1 to 3: 1.
The magnesium alkoxide compound may be the reaction product of an alcohol as defined above with a magnesium compound selected from the group consisting of dialkyl magnesium, alkyl magnesium alkoxide, dialkoxy magnesium, alkoxy magnesium halide and alkyl magnesium halide. In addition, dialkoxymagnesium, diaryloxymagnesium, aryloxymagnesium halide, aryloxymagnesium, and alkylaryloxymagnesium may be used. The alkyl groups in the magnesium compound may be the same or different C1-C20Alkyl, preferably C2-C10An alkyl group. The alkylmagnesium alkoxide compounds, when used, are typically magnesium ethylbutoxide, magnesium butylpentanoate, magnesium octylbutoxide, and magnesium octyloctoxide. Preferably, a magnesium dialkyl is used. The most preferred magnesium dialkyl is butyl octyl magnesium or butyl ethyl magnesium.
In addition to the reaction with the alcohols (A) and (B), the magnesium compounds may also be reacted with a compound of the formula R' (OH)mTo obtain the magnesium alkoxide compound. If used, the polyols are preferably the following alcohols: wherein R' is a linear, cyclic or branched C2-C10A hydrocarbon residue and m is an integer from 2 to 6.
The magnesium alkoxide compound of step a) is thus selected from: dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide, aryloxymagnesium halide, alkylmagnesium alkoxide, arylmagnesium alkoxide, alkylmagnesium aryloxide, or a mixture of magnesium dihalide and dialkoxymagnesium.
The solvent used to prepare the catalyst of the invention may be selected from: aromatic and aliphatic linear, branched and cyclic hydrocarbons or mixtures thereof having from 5 to 20 carbon atoms, preferably from 5 to 12 carbon atoms. Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane and nonane. Particular preference is given to hexane and pentane.
The reaction for preparing the magnesium alkoxide compound may be carried out at 40 to 70 ℃. The person skilled in the art knows how to select the optimum temperature depending on the magnesium compound and the alcohol used.
The group 4 to 6 Transition Metal (TM) compound defined by IUPAC version 2013 is preferably a titanium compound, most preferably a titanium halide, such as TiCl4。
The non-phthalic Internal Donor (ID) used to prepare the particular type of Ziegler-Natta catalyst used in the present invention is preferably selected from: non-o-phthalic (di) carboxylic acid (di) esters, 1, 3-diethers, and derivatives and mixtures thereof. Particularly preferred donors are diesters of monounsaturated non-phthalic dicarboxylic acids, in particular esters belonging to the following group: including malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1, 2-dicarboxylates and benzoates and any derivatives and/or any mixtures thereof. Preferred examples are, for example, substituted maleates and citraconates, with citraconate being most preferred.
Here and hereinafter, the term "derivative" includes substituted compounds.
In the emulsion-solidification process, a liquid-liquid two-phase system may be formed as follows: simply stirred and optionally added with one or more (other) solvents and/or additives, such as turbulence reducing agents (TMAs) and/or emulsifiers and/or emulsion stabilizers, such as surfactants, and used in a manner known in the art. These solvents and/or additives are used to facilitate the formation of and/or stabilize the emulsion. Preference is given toThe surfactant is an acrylic or methacrylic polymer. Particular preference is given to unbranched C12-C20(meth) acrylates, such as poly (hexadecyl methacrylate) and poly (octadecyl methacrylate), and mixtures thereof. The turbulence reducing agent (TMA), if used, is preferably selected from polymers of alpha-olefin monomers having 6 to 20 carbon atoms, such as polyoctene, polynonane, polydecene, polyundecene or polydodecene or mixtures thereof. Polydecene is most preferred.
The solid particulate product obtained by the deposition process or the emulsion-solidification process may be washed at least once, preferably at least twice, most preferably at least three times. The washing can be carried out using aromatic and/or aliphatic hydrocarbons, preferably using toluene, heptane or pentane. TiCl may also be used4Optionally in combination with aromatic and/or aliphatic hydrocarbons. The cleaning solution may also contain a donor and/or a group 13 compound, such as a trialkylaluminum, a halogenated alkylaluminum compound, or an aluminum alkoxide compound. The aluminum compound may also be added during the catalyst synthesis. The catalyst may be further dried, for example by evaporation or flash evaporation with nitrogen, or slurried into an oily liquid without any drying step.
The particular type of Ziegler-Natta catalyst ultimately obtained is desirably obtained in particulate form, generally having an average particle size of from 5 to 200 μm, preferably from 10 to 100 μm. The particles are generally of low dense porosity, typically less than 20g/m2More preferably less than 10g/m2Surface area of (a). Typically, the amount of Ti present in the catalyst is from 1 to 6 wt%, the amount of Mg is from 10 to 20 wt%, and the amount of internal donor present in the catalyst is from 10 to 40 wt% of the catalyst component. The preparation of the catalysts used according to the invention is described in detail in WO2012/007430, EP2610271 and EP2610272, which are incorporated herein by reference.
The External Donor (ED) is preferably present as an additional component in the polymerization process. Suitable External Donors (ED) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and mixtures thereof. The use of silanes is particularly preferred. Most preferably, silanes of the following general formula (I) are used:
Ra pRb qSi(ORc)(4-p-q) (I)
wherein R isa、RbAnd RcRepresents a hydrocarbon residue, in particular an alkyl or cycloalkyl group, p and q are numbers in the range from 0 to 3 and their sum (p + q) is equal to or less than 3. Ra、RbAnd RcEach independently selected and may be the same or different. Specific examples of silanes corresponding to the general formula (I) are di-tert-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane and dicyclopentyldimethoxysilane. Another most preferred silane corresponds to the following general formula (II):
Si(OCH2CH3)3(NR3R4) (II)
wherein R is3And R4May be the same or different and represent a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms. Particularly preferred is R3And R4Each independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl. Most preferably, ethyl is used.
Typically, in addition to a ziegler-natta catalyst or a specific type of ziegler-natta catalyst and optionally an External Donor (ED), a co-catalyst may be used. The cocatalyst is preferably a compound of group 13 of the periodic Table (IUPAC version 2013), for example an aluminum compound, such as an organoaluminum or aluminum halide compound. Examples of suitable organoaluminum compounds are alkylaluminum compounds or halogenated alkylaluminum compounds. Thus, in one embodiment, the cocatalyst (Co) is a trialkylaluminum (e.g. Triethylaluminum (TEAL)), a dialkylaluminum chloride or an alkylaluminum dichloride or a mixture thereof. In one embodiment, the cocatalyst (Co) is Triethylaluminum (TEAL).
Generally, the ratio of promoter (Co) to External Donor (ED) [ Co/ED ] and/or the ratio of promoter (Co) to Transition Metal (TM) [ Co/TM ] are finely selected for each process. The ratio of cocatalyst (Co) to External Donor (ED) [ Co/ED ] is suitably from 3.0 to 45.0mol/mol, preferably from 4.0 to 35.0mol/mol, more preferably from 5.0 to 30.0 mol/mol. A suitable lower limit may be 3.0mol/mol, preferably 4.0mol/mol, more preferably 5.0 mol/mol. A suitable upper limit may be 45.0mol/mol, preferably 35.0mol/mol, more preferably 30.0 mol/mol. The upper and lower limits of the range are included.
The ratio [ Co/TM ] of the cocatalyst (Co) to the Transition Metal (TM) may suitably be in the range of from 40.0 to 500mol/mol, preferably from 50.0 to 400mol/mol, more preferably from 60.0 to 350 mol/mol. A suitable lower limit may be 40.0mol/mol, preferably 50.0mol/mol, more preferably 60.0 mol/mol. A suitable upper limit may be 500mol/mol, preferably 400mol/mol, more preferably 350 mol/mol. The upper and lower limits of the range are included.
The present invention also provides articles comprising the polypropylene composition of the present invention. Suitable articles comprising the polypropylene composition of the present invention are films, e.g. films for flexible packaging systems, such as ordinary food packaging bags or pouches (pouch).
Preferred articles are monolayer or multilayer films, obtainable by any method known to the skilled person, such as cast film techniques or blown film techniques. The film is preferably used as a sealant layer in a multilayer film structure, preferably as a very thin sealant layer at the uppermost part of the multilayer structure.
Thus, the present invention also relates to an article comprising at least 70 wt%, preferably at least 80.0 wt%, more preferably at least 90.0 wt%, even more preferably at least 95.0 wt%, yet more preferably at least 99.0 wt% of the polypropylene composition of the present invention.
Finally, the present invention relates to the use of the polypropylene composition according to the invention for the manufacture of an article, a film or a multilayer film.
Examples
I. Measuring method
The following definitions of terms and determination methods apply to the above general description of the invention as well as to the examples below, unless otherwise defined.
a) Melt flow rate
The Melt Flow Rate (MFR) is determined according to ISO 1133 and is characterized in g/10 min. MFR is an indication of the flowability and thus the processability of the polymer. The higher the melt flow rate, the lower the polymer viscosity. MFR of Polypropylene2Measured at 230 ℃ under a load of 2.16 kg.
b) Melt Flow Rate (MFR) of propylene terpolymer (PPF2)2)
MFR of propylene terpolymer (PPF2)2The following equation is used for the calculation:
ln (MFR of the Polypropylene composition)2) MFR of ═ x (ln (propylene copolymer (PPF 1)) (MFR)2) () + (1-x) (ln (MFR of propylene terpolymer (PPF 2)))2))；
Wherein the MFR of the polypropylene composition2Means the MFR of the PP composition of the invention2And wherein x ═ propylene copolymer (PPF1) is based on the combined weight of propylene copolymer (PPF1) and propylene terpolymer (PPF2) (total of 1) in weight ratio (wt).
c) Melting temperature
The melting temperature Tm was determined by Differential Scanning Calorimetry (DSC) according to ISO11357-3 using a dual sample cell TA instrument 2920 with an RSC refrigeration unit and a data processing station. Heating and cooling rates of 10 deg.C/min were employed in the heating/cooling/heating cycle between +23 deg.C and +210 deg.C. The melting temperature (Tm) is determined in the second heating step.
d) Xylene cold soluble fraction (XS, wt%)
The amount of polymer soluble in xylene is determined according to ISO 16152 (fifth edition, 2005-07-01) at 25 ℃.
e) Comonomer content
Using a Bruker Advance III 500NMR spectrometer for1H and13c was run at 500.13MHz and 125.76MHz respectively, and quantification was recorded in the molten state13C{1H } NMR spectrum. For all pneumatic units nitrogen was used, using at 180 ℃13C optimization a 7mm magic angle rotating (MAS) probe recorded all spectra. About 200mg of material was loaded into a zirconia MAS rotor with an outer diameter of 7mm and rotated at 4 kHz. The settings were chosen primarily to achieve the high sensitivity required for rapid identification and accurate quantification klimkike 06, parkinson07, cartignoles 09. Using a standard single pulse excitation, NOE was used with a short cyclic delay of 3 seconds { pollard04, klimke06} and an RS-HEPT decoupling scheme { fililip 05, griffin07} was applied. To pairA total of 1024(1k) transients were obtained for each spectrum.
For quantitative determination13C{1H NMR spectra were processed, integrated, and the associated quantification performance was determined from the integration. All chemical shifts are referenced internally to methyl isotactic pentads (mmmm) at 21.85 ppm.
A characteristic signal corresponding to the 1-butene incorporation was observed and the comonomer content was quantified in the following manner: quantification of 1-butene introduced at intervals in the PBP sequence was performed using the integral of the number of α B2 sites at 43.6ppm based on the number of reported sites per comonomer:
B＝IαB2/2
quantification of 1-butene continuously introduced in the PBBP sequence was performed using the integral of the number of α α B2 sites at 40.5ppm to the number of reported sites per comonomer:
BB＝2*IααB2
based on the sum of the 1-butene introduced intermittently and introduced continuously, the total content of 1-butene was calculated:
Btotal amount of＝B+BB
A characteristic signal corresponding to the ethylene incorporation was observed and the comonomer content was quantified in the following manner. And quantifying ethylene introduced at intervals in the PEP sequence by utilizing the integral of the number of reported sites of each comonomer occupied by the S alpha gamma site at 37.9 ppm:
E＝ISαγ/2
when a characteristic signal corresponding to the continuous introduction of ethylene in the PEEP sequence is observed, S at 27ppm is usedβδThe integration of sites over the number of reported sites per comonomer quantifies the ethylene continuously introduced:
EE＝ISβδ
when no sites indicating continuous incorporation of ethylene in the PEEE sequence were observed, the total ethylene comonomer content was calculated as follows:
Etotal amount of＝E+EE
No characteristic signal Resconi00 corresponding to a zone defect was observed.
Propylene was quantified based on the predominant S α methylene site at 46.7ppm and compensated for the relative amount of methylene units of propylene in the unaccounted PBP, PBBP, PEP and PEEP sequences:
Ptotal amount of＝ISαα+B+BB/2+E+EE/2
Thus, the total mole fraction of 1-butene in the polymer is calculated as follows:
fB＝Btotal amount of/(ETotal amount of+PTotal amount of+BTotal amount of)
Thus, the total mole fraction of ethylene in the polymer is calculated as follows:
fE＝Etotal amount of/(ETotal amount of+PTotal amount of+BTotal amount of)
The mole percent comonomer incorporation was calculated according to the mole fractions as follows:
B[mol％]＝100*fB
E[mol％]＝100*fE
the weight percent comonomer incorporation was calculated according to the mole fractions as follows:
B[wt％]＝100*(fB*56.11)/((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))
E[wt％]＝100*(fE*28.05)/((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))
klimke06-Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.
parkinson07-Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.
pollard04-Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.
filip05-Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239
griffin07-Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.in Chem.2007 45,S1,S198
castignolles09-Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373
busico01-Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443
busico97-Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L.,Macromoleucles 30(1997)6251
zhou07-Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225
busico07-Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128
resconi00-Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253
the comonomer content of the propylene terpolymer (PPF2) was calculated using the following equation:
the comonomer content of the polypropylene composition ═ x (comonomer content of propylene copolymer (PPF1) + (1-x) (comonomer content of propylene terpolymer (PPF 2)).
x ═ weight ratio (wt) of propylene copolymer (PPF1) based on the total weight of propylene copolymer (PPF1) and propylene terpolymer (PPF2) (total of 1).
f) Seal Initiation Temperature (SIT), seal Range
Differential Scanning Calorimetry (DSC) experiments were performed according to ISO 11357/1 on a TA instruments Q2000 apparatus calibrated with indium, zinc and tin. Measurements were made according to ISO 11357/3 on 5. + -. 0.5mg samples at a scan rate of 10 ℃/min between-30 ℃ and 225 ℃ under a nitrogen atmosphere (50ml/min) according to a heating/cooling/heating cycle. The temperatures at which the endotherm and the exotherm peaked in the cooling cycle and the second heating cycle, respectively, were taken as the melting temperature (Tm) and the crystallization temperature (Tc).
Predicting a Seal Initiation Temperature (SIT) by analyzing the second heating sweep according to the following steps: the first boundary of the integration was set at 16 deg.c, the second boundary of the integration was set at Tm +20 deg.c, and the total enthalpy of fusion was recorded. The temperature T1 is defined as the temperature at which 19% of the melting enthalpy with the above-mentioned integral boundary is reached. The parameter SIT is finally calculated as follows:
SIT＝1.0596×T1+3.8501
inventive and comparative examples
a) Preparation of the catalyst
3.4 liters of 2-ethylhexanol and 810 ml of propylene glycol monobutyl ether (molar ratio 4/1) were charged to a 20.0 liter reactor. Then, 7.8 liters of a 20.0% solution of BEM (butylethylmagnesium) in toluene supplied by Crompton GmbH was slowly added to the well stirred alcohol mixture. During the addition, the temperature was maintained at 10.0 ℃. After the addition, the temperature of the reaction mixture was raised to 60.0 ℃ and mixing was continued at this temperature for 30 minutes. Finally, after cooling to room temperature, the resulting magnesium alkoxide was transferred to a storage vessel.
21.2g of the magnesium alkoxide prepared above was mixed with 4.0 ml of bis (2-ethylhexyl) citraconate for 5 minutes. The Mg complex obtained is subsequently used for the preparation of the catalyst component after mixing.
19.5 ml of titanium tetrachloride were placed in a 300 ml reactor equipped with a mechanical stirrer at 25.0 ℃. The mixing speed was adjusted to 170 rpm. The temperature was maintained at 25.0 ℃ and 26.0g of the magnesium complex prepared above was added over 30 minutes. 3.0 ml of the solution is added
Figure BDA0002091820590000151
1-254 and 1.0 ml of a solution containing 2mg of Necadd 447TMA toluene solution of (2). 24.0 ml of heptane were then added to form an emulsion. Mixing was continued at 25.0 ℃ for 30 minutes, after which the reactor temperature was raised to 90.0 ℃ over 30 minutes. The reaction mixture was stirred at 90 ℃ for a further 30 minutes. After this time, the stirring was stopped, and the reaction mixture was allowed to stand at 90.0 ℃ for 15 minutes. The solid material was washed 5 times: washing was carried out at 80.0 ℃ for 30 minutes with stirring at 170 rpm. After the stirring was stopped, the reaction mixture was allowed to stand for 20 to 30 minutes and then siphoned.
Cleaning 1: a mixture of 100 ml of toluene and 1 ml of donor was used for washing.
And (3) cleaning 2: 30 ml of TiCl are used4And 1 ml donor.
And (3) cleaning: the washing was performed using 100 ml of toluene.
And (4) cleaning: the washing was performed using 60 ml heptane.
And (5) cleaning: the washing was carried out with 60 ml of heptane under stirring for 10 minutes.
The stirring was then stopped and the reaction mixture was allowed to stand for 10 minutes while the temperature was reduced to 70 ℃, after which siphoning was performed followed by 20 minutes of nitrogen sparging to form an air sensitive powder.
b) Inventive embodiments (IE1 and IE2)
Inventive Example (IE) was prepared in a pilot plant with a prepolymerization reactor, a slurry loop reactor and a gas phase reactor. The solid catalyst component described above was used in inventive examples IE1 and IE2 using Triethylaluminum (TEAL) as co-catalyst and dicyclopentyldimethoxysilane (D-donor) as external donor.
c) COMPARATIVE EXAMPLE (CE1 and CE2)
CE-1 is C2C4Propylene terpolymer having a medium molecular weight distribution, MFR of 6.0g/10min2A melting point of 130 ℃, a Seal Initiation Temperature (SIT) of 103 ℃ and is manufactured and sold by Borealis under the trade name TD310 BF.
CE-2 is C2C4Propylene terpolymer having a medium molecular weight distribution, MFR of 6.0g/10min2A melting point of 130 ℃, a Seal Initiation Temperature (SIT) of 103 ℃ and is manufactured and sold by Borealis under the trade name TD210 BF.
TABLE 1 polymerization conditions
IE-1 IE2 IE3
Loop current (propylene polymer component PPF1)
Temperature of [℃] 65 70 70
Pressure of [kPa] 5311 5251 2580
Residence time [h] 0.4 0.46 0.4
Ratio of [％] 38 40 47
H2/C3Ratio of [mol/kmol] 2.2 0.6
C4/C3Ratio of [mol/kmol] 79.9
MFR2 [g/10min] 4.5 4.7 6.7
XS [wt％] 4.3 3.5
C4Content (wt.) [mol％] 4.00 4.00 5.30
GPR1 (propylene Polymer component PPF2)
Temperature of [℃] 75 75 75
Pressure of [kPa] 2300 2400 1800
Residence time [h] 1.5 2.1 1.6
Ratio of [％] 62 60 53
H2/C3Ratio of [mol/kmol] 23.4 14.4
C2/C3Ratio of [mol/kmol] 25 15.2
C4/C3Ratio of [mol/kmol] 205 141.1 412
C2Content (wt.) [mol％] 5.00 3.00 3.10
C4Content (wt.) [mol％] 7.50 8.20 14.60
Polypropylene composition
MFR2 [g/10min] 5 5.2 5.7
XS [wt％] 25 22 36
C4Sum of contents [mol％] 6.10 6.50 10.20
C2Sum of contents [mol％] 3.10 1.80 1.60
Melting Point [℃] 142.3 141.8 142.9
TABLE 2 melting temperature (Tm), Seal Initiation Temperature (SIT) and Delta values for inventive examples (IE1, IE2, IE3) and comparative examples (CE1, CE2)
IE1 IE2 IE3 CE1 CE2
Tm 142.3 141.8 142.9 133.2 132.8
SIT[℃] 97.5 99.1 98 104 106
△(Tm-SIT) 44.8 42.7 44.9 29 27
From Table 2 it follows that the polypropylene compositions according to the invention have higher melting temperature (Tm) values and higher Delta (Tm-SIT) values than the comparative examples.

Claims (15)

1. Polypropylene composition comprising a binary blend of two propylene polymer components PPF1 and PPF2, said two components being present in the following specified amounts:
a) less than or equal to 50 wt% of propylene polymer groupContains PPF1 which is propylene copolymer containing propylene monomer and 1.50-7.00 mol% of C4-C10A comonomer of an alpha-olefin, and
b) greater than or equal to 50 wt% of a propylene polymer component PPF2 which is a propylene terpolymer comprising propylene monomer, from 3.00 to 12.00 mol% of ethylene comonomer and from 1.50 to 17.00 mol% of a comonomer selected from C4-C10One of the comonomers of the alpha-olefin,
wherein the polypropylene composition:
i. has a melting temperature (Tm) in the range of 140 to 150 ℃ as determined by DSC according to ISO11357, and
satisfying the following equation:
△＝Tm-SIT
wherein Δ is in the range of 41 to 46 ℃, and wherein
Tm is the melting temperature of the polypropylene composition in units of,
SIT is the seal initiation temperature of the polypropylene composition in degrees Celsius, calculated from the pellets by DSC analysis,
wherein the amounts of PPF1 and PPF2 are calculated relative to the total amount of the propylene polymer components PPF1 and PPF 2.
2. The polypropylene composition of claim 1, wherein said polypropylene composition has an MFR in the range of 3.0 to 10.0g/10min, measured according to ISO 1133 at 230 ℃ and 2.16kg load2。
3. The polypropylene composition according to any one of claims 1 to 2, wherein said polypropylene composition has a xylene soluble amount in the range of 15 to 40 wt%, measured according to ISO 16152 on year 2005, 07, 01, 5 th edition at 25 ℃.
4. The polypropylene composition according to any one of claims 1 to 2, wherein said composition is obtained in the presence of a Ziegler-Natta catalyst.
5. The polypropylene composition according to any one of claims 1 to 2, wherein said Ziegler-Natta catalyst is free of phthalic acid based compounds.
6. The polypropylene composition according to any one of claims 1 to 2, wherein said propylene polymer component PPF1 is a propylene copolymer comprising 1-butene and said propylene polymer component PPF2 is a propylene terpolymer comprising ethylene comonomer and 1-butene.
7. A process for the preparation of the polypropylene composition of claim 1 by a sequential polymerization process comprising at least two reactors in series, said process comprising the steps of:
in the first reactor R-1, which is a slurry reactor, propylene and a catalyst selected from the group consisting of C4-C10A comonomer of an alpha-olefin is polymerized to give the propylene polymer component PPF1,
transferring the propylene polymer component PPF1 and unreacted comonomer from the first reactor R-1 to a second reactor R-2, which is a first gas phase reactor GPR-1,
in the first gas phase reactor GPR-1, propylene, ethylene and a gas phase catalyst selected from the group consisting of C4-C10Polymerizing one comonomer of an alpha-olefin in the presence of the propylene polymer component PPF1 to obtain the propylene polymer component PPF2, the propylene polymer component PPF2 and the propylene polymer component PPF1 forming a polypropylene composition,
recovering the polypropylene composition.
8. The process of claim 7, wherein the slurry reactor is a loop reactor.
9. An article comprising the polypropylene composition according to any one of claims 1 to 6.
10. A film comprising the polypropylene composition according to any one of claims 1 to 6.
11. The film of claim 10, wherein the film is a blown film or a cast film.
12. The film of any one of claims 10 to 11, wherein the film is a multilayer film.
13. Use of the polypropylene composition according to any one of claims 1 to 6 for the manufacture of an article.
14. Use of the polypropylene composition according to any one of claims 1 to 6 for the manufacture of a film.
15. The use of claim 14, wherein the film is a multilayer film.
CN201780076833.8A 2016-12-29 2017-12-19 Polypropylene composition with low seal initiation temperature and high melting temperature Active CN110072897B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP16207307 2016-12-29
EP16207307.6 2016-12-29
PCT/EP2017/083486 WO2018122033A1 (en) 2016-12-29 2017-12-19 Polypropylene composition combining low sealing initiation temperature and high melting temperature

Publications (2)

Publication Number Publication Date
CN110072897A CN110072897A (en) 2019-07-30
CN110072897B true CN110072897B (en) 2021-11-02

Family

ID=57680154

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780076833.8A Active CN110072897B (en) 2016-12-29 2017-12-19 Polypropylene composition with low seal initiation temperature and high melting temperature

Country Status (7)

Country Link
US (1) US10487203B2 (en)
EP (1) EP3562848B1 (en)
KR (1) KR102037645B1 (en)
CN (1) CN110072897B (en)
ES (1) ES2940416T3 (en)
RU (1) RU2723096C1 (en)
WO (1) WO2018122033A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2724050C1 (en) * 2016-12-29 2020-06-19 Бореалис Аг Polypropylene-based composition having low welding start temperature and high melting point
EP3453727A1 (en) * 2017-09-08 2019-03-13 Borealis AG Process for preparing polypropylene composition
WO2020099566A1 (en) * 2018-11-15 2020-05-22 Borealis Ag Propylene butene copolymer
US20210395427A1 (en) * 2018-11-15 2021-12-23 Borealis Ag Propylene butene copolymer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1061031A (en) * 1990-09-28 1992-05-13 希蒙特公司 The crystaline polypropylene polymer composition that heat-seal temperature is low
CN101255256A (en) * 2007-02-01 2008-09-03 住友化学株式会社 Propylene-based copolymer material, film made therefrom, and method for producing propylene-based copolymer material
CN103080211A (en) * 2010-09-06 2013-05-01 巴塞尔聚烯烃意大利有限责任公司 Polyolefin compositions having improved sealability
EP3064548A1 (en) * 2015-03-02 2016-09-07 Borealis AG Polypropylene composition combining low sealing initiation temperature, low haze, low hexane solubles and improved tear resistance and melting temperature.
WO2016198601A1 (en) * 2015-06-12 2016-12-15 Borealis Ag Process for producing propylene polymer compositions

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI86867C (en) 1990-12-28 1992-10-26 Neste Oy FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN
FI111848B (en) 1997-06-24 2003-09-30 Borealis Tech Oy Process and equipment for the preparation of homopolymers and copolymers of propylene
FI980342A0 (en) 1997-11-07 1998-02-13 Borealis As Polymerroer och -roerkopplingar
FI974175A (en) 1997-11-07 1999-05-08 Borealis As Process for producing polypropylene
BR9915469B1 (en) * 1998-08-20 2009-01-13 crystalline propylene copolymer compositions, process for preparing copolymer compositions and monolayer or multilayer film or sheet comprising said polymeric compositions.
FI991057A0 (en) 1999-05-07 1999-05-07 Borealis As High stiffness propylene polymers and process for their preparation
MY132768A (en) * 2001-10-09 2007-10-31 Basell Poliolefine Italia Spa Crystalline propylene copolymer compositions having improved sealability and optical properties and reduced solubility.
ATE499392T1 (en) 2002-06-25 2011-03-15 Borealis Tech Oy POLYOLEFIN WITH IMPROVED SCRATCH RESISTANCE AND METHOD FOR PRODUCING IT
EP1484343A1 (en) 2003-06-06 2004-12-08 Universiteit Twente Process for the catalytic polymerization of olefins, a reactor system and its use in the same process
WO2011064119A1 (en) 2009-11-24 2011-06-03 Basell Poliolefine Italia S.R.L. Polyolefin compositions having a low seal temperature and improved hot tack
ES2525554T3 (en) 2010-07-13 2014-12-26 Borealis Ag Catalyst component
ES2727405T3 (en) 2011-12-30 2019-10-16 Borealis Ag Preparation of phthalate free ZN PP catalysts
EP2610272B1 (en) 2011-12-30 2017-05-10 Borealis AG Catalyst component

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1061031A (en) * 1990-09-28 1992-05-13 希蒙特公司 The crystaline polypropylene polymer composition that heat-seal temperature is low
CN101255256A (en) * 2007-02-01 2008-09-03 住友化学株式会社 Propylene-based copolymer material, film made therefrom, and method for producing propylene-based copolymer material
CN103080211A (en) * 2010-09-06 2013-05-01 巴塞尔聚烯烃意大利有限责任公司 Polyolefin compositions having improved sealability
EP3064548A1 (en) * 2015-03-02 2016-09-07 Borealis AG Polypropylene composition combining low sealing initiation temperature, low haze, low hexane solubles and improved tear resistance and melting temperature.
WO2016198601A1 (en) * 2015-06-12 2016-12-15 Borealis Ag Process for producing propylene polymer compositions

Also Published As

Publication number Publication date
CN110072897A (en) 2019-07-30
EP3562848B1 (en) 2023-02-08
WO2018122033A1 (en) 2018-07-05
US10487203B2 (en) 2019-11-26
KR102037645B1 (en) 2019-10-29
ES2940416T3 (en) 2023-05-08
KR20190084340A (en) 2019-07-16
US20190309150A1 (en) 2019-10-10
EP3562848A1 (en) 2019-11-06
RU2723096C1 (en) 2020-06-08

Similar Documents

Publication Publication Date Title
EP3562849B1 (en) Process for preparing polypropylene composition
CN110072897B (en) Polypropylene composition with low seal initiation temperature and high melting temperature
CN111032708B (en) Process for preparing polypropylene composition
CN113366038A (en) Bimodal terpolymers
CN110062776B (en) Polypropylene composition with low seal initiation temperature and high melting temperature
CN113366037A (en) Polypropylene composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant